Fabrication of substrates with a useful layer of monocrystalline semiconductor material

ABSTRACT

The invention relates to methods for fabricating a semiconductor substrate. In one embodiment, the method includes providing an support that includes a barrier layer thereon for preventing loss by diffusion of elements derived from dissociation of the support at epitaxial growth temperatures; providing a seed layer on the barrier layer, wherein the seed layer facilitates epitaxial growth of a single crystal III-nitride semiconductor layer thereon; epitaxially growing a nitride working layer on the thin seed layer; and removing the support to form the substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of application Ser. No. 12/984,895filed Jan. 5, 2011, which is a continuation-in-part of application Ser.No. 11/831,484 filed Jul. 31, 2007, now U.S. Pat. No. 7,888,235, whichis a division of application Ser. No. 10/883,437 filed on Jul. 1, 2004,now U.S. Pat. No. 7,265,029, which is (a) a continuation of applicationSer. No. 10/458,471 filed on Jun. 9, 2003, abandoned, and (b) acontinuation-in-part of application Ser. No. 10/446,605, filed on May27, 2003, now U.S. Pat. No. 6,794,276, which is a continuation ofInternational application no. PCT/FR01/03714 filed Nov. 26, 2001. Theentire content of each prior application is expressly incorporatedherein by reference thereto.

FIELD OF THE INVENTION

The present invention relates to methods of fabricating a semiconductorsubstrate. In an embodiment, the semiconductor substrate includes atleast one layer of monocrystalline semiconductor material, especially awide band gap material, and in particular a mono or poly-metallicnitride substrate, such as gallium nitride (GaN), indium gallium nitride(InGaN), or aluminum nitride (AlN), or a diamond substrate, on a targetsubstrate.

BACKGROUND OF THE INVENTION

Semiconductor technology based on the use of GaN, AlN, and compoundsthereof as semiconductor material, currently suffer from a lack oflarge-sized bulk substrates of such materials.

The most widely known technique for producing a bulk GaN substrateconsists of depositing the GaN on a substrate by a process known ashetero-epitaxy.

In order to produce a substrate having good crystal quality, thesubstrate material and the epitaxial monocrystal to be depositedthereon, must have little lattice mismatch. Additionally, the thermalexpansion coefficient of both the substrate material and the epitaxialmonocrystal must be relatively similar, because the high temperaturesinvolved in hetero-epitaxy is known to sometimes cause dissociation anddiffusion of elements of the substrate to the epitaxial layer. Thirdly,the substrate material must be mechanically and chemically stable athigh temperatures so as to obtain good crystal quality. Naturally,qualities such as surface condition and crystal quality of the startingsubstrate are also important factors.

Currently, sapphire and silicon carbide (SiC) are commonly used as thesubstrate material. However, sapphire and silicon carbide are far frombeing optimal substrate material due to their lattice parameters andtheir expansion coefficients.

Another common practice is growing layers of GaN on substrates such aszirconium oxide (ZnO), lithium gallium oxide (LiGaO₂), lithium aluminumoxide (LiAlO₂) (See “Growth of III-Nitrides on ZnO, LiGaO₂ and LiAlO₂substrates”, Mackenzie et al., J. Electrochem. Soc., vol. 145, No. 7,July 1998, p. 2581) or of neodymium gallium oxide (NdGaO₃) (see “GaNbulk substrates for GaN based LEDs and LDs”, Oda et al., Phys. Stat.Sol., (a) 180, 51 (2000). Although these substrate materials are oftenselected for their small lattice mismatch and their similar coefficientof expansion with GaN, they suffer from having poor chemical stabilityunder high temperatures as compared to sapphire or silicon carbide. Forexample, when the oxide substrates are exposed to high temperatures,dissociation of the metal and/or the oxygen occurs and such dissociatedmetal and/or oxygen diffuses to the epitaxial layer. As described inImpurity contamination of GaN epitaxial films from the sapphire, SiC,and ZnO substrates, Popovici et al., Appl. Phys. Lett., 71 (23), 8 Dec.1997, and incorporated herein, contamination of the epitaxial layer byzinc and oxygen from a ZnO substrate compromises the quality and purityof the epitaxial layer.

Furthermore, once the layer or layers intended to form the substratehave been formed, in the majority of cases the support on which growthhas been carried out has to be removed, which necessitates eitherchemical attack of said support and thus its loss even if it is producedfrom an expensive material, thereby increasing the cost of the process,or by rupture between the layers formed by epitaxial growth and saidsupport, which can be difficult to control and/or can necessitateparticular dispositions which complicate the method or make it moreexpensive.

More generally, it has been proven that, for the purpose of temporarysupport removal, chip manufacturers mostly prefer an etching techniquerather than a rupturing technique. This is mainly because, in thesemiconductor industry, etching techniques have been mastered for yearsand most often do not require any additional investment while rupturetechniques are more difficult to control or require significant capitalinvestment, thus adding complexity to the process.

An additional technique for separating the support and the substratesgenerates stress at the boundary between the support and the substrateby means of laser illumination. Illuminating the support-substrate wafercan generate sufficient stress at the boundary to cause layerseparation. Stress can be generated by phase transition, gas evolution,vaporization or sublimation. It is advantageous for one of the supportor the substrate to be significantly transparent at the laser wavelengthand the other to be significantly absorbent so that absorption of thelaser radiation is concentrated at their boundary. See, e.g., U.S. Pat.No. 6,372,608 B1 (especially FIG. 23).

In parallel, an etching approach would be valuable only if the materialof the support is relatively inexpensive, but such inexpensivematerials, such as gallium Arsenide GaAs, introduce additionaldrawbacks. In this regard, the article “Preparation of largefreestanding GaN substrates by Hydride Vapor Phase Epitaxy using GaAs asa starting substrate”, Motoki et al., Jpn. J. Appl. Phys., Vol. 41(2001), p. 140-143, proposes using a gallium arsenide GaAs substrate onwhich to grow GaN by hetero-epitaxy. However, when heated to the hightemperatures involved in epitaxy, GaAs undergoes surface dissociation,which causes arsenic to evaporate, which can contaminate the GaNmonocrystal.

The present invention now seeks to overcome these disadvantages.

SUMMARY OF THE INVENTION

The invention relates to methods for fabricating a semiconductorsubstrate. In an implementation, the method includes providing anintermediate support, providing a nucleation layer, and optionally butpreferably providing at least one bonding layer between the intermediatesupport and the nucleation layer to improve the bonding energy therebetween, and to form an intermediate assembly. The technique alsoincludes providing at least one layer of a semiconductor material uponthe nucleation layer, bonding a target substrate to the depositedsemiconductor material to form a support assembly that includes thetarget substrate, the deposited semiconductor material, and theintermediate assembly, and then processing the support assembly toremove the intermediate assembly. The result is a semiconductorsubstrate that includes the at least one layer of semiconductor materialon the target substrate.

Preferably, the nucleation layer functions as a barrier layer againstdiffusion of atoms from the intermediate support at epitaxial growthtemperatures, and the semiconductor material layer is epitaxiallydeposited on the nucleation layer. If desired, a second barrier layermay be provided between the nucleation layer and the intermediatesupport prior to epitaxially depositing the semiconductor materiallayer. In an advantageous embodiment, the intermediate support includesa barrier layer that is resistant to diffusing elements derived fromdissociation of the intermediate support at epitaxial growthtemperatures, and the semiconductor material is epitaxially deposited onthe nucleation layer. The barrier layer may be formed by a depositiontechnique, and in an implementation, the barrier layer is first appliedto the intermediate support and then the nucleation layer is applied tothe barrier layer. A layer of adhesive may be applied to at least one ofa surface of the barrier layer or a surface of the nucleation layer todefine a bonding layer.

The intermediate assembly is advantageously provided by implantingatomic species into at least a portion of a source substrate to definethe nucleation layer, wherein a main concentration of implanted atomicspecies defines a detachment zone, applying the at least one bondinglayer to at least one of a surface of the nucleation layer or to atleast a portion of a surface of the intermediate support, attaching thesource substrate implanted with the atomic species, the at least onebonding layer, and at least a portion of the intermediate supporttogether to form a structure, and treating the structure to detach theintermediate assembly from the source substrate at the detachment zone.

According to this aspect of the invention, the intermediate support ispreferably selected from the group consisting of silicon, galliumarsenide, zinc oxide, lithium gallium oxide and lithium aluminum oxide.In addition, the nucleation layer may include at least one of siliconcarbide, gallium nitride, or sapphire. The semiconductor material alsopreferably is made of at least one of a mono or poly-metallic nitride,and in particular gallium nitride. The nucleation layer is preferablyselected from the group consisting of silicon carbide, gallium nitrideand sapphire. If desired, the final support assembly may further includea reflective coating.

Preferably, the at least one bonding layer is made of at least one ofsilicon oxide or silicon nitride. The target substrate may be made of atleast one of monocrystalline or polycrystalline silicon. Advantageously,the final support is chemically treated to remove at least one of theintermediate support or the nucleation layer.

Another embodiment of the invention relates to a method of making asemiconductor substrate which comprises providing an support thatincludes a barrier layer thereon for preventing loss by diffusion ofelements derived from dissociation of the support at epitaxial growthtemperatures; providing a seed layer on the barrier layer, wherein theseed layer facilitates epitaxial growth of a single crystal III-nitridesemiconductor layer thereon; epitaxially growing a nitride working layeron the thin seed layer; and removing the support to form the substrate.

The support for this embodiment is typically made of a sintered orpolycrystalline material, and preferably a polycrystalline siliconcarbide, monocrystalline silicon carbide, polycrystalline aluminumnitride, polycrystalline gallium nitride, or monocrystalline galliumnitride having a concentration of dislocation that is greater than10⁷/cm². The barrier layer generally comprises silicon nitride, whilethe seed layer comprises sapphire, silicon carbide, zinc oxide, silicon,gallium nitride, neodymium gallate, or lithium gallate. The seed layerpreferably comprises a material with a crystal lattice parameterselected so that the nitride working layer has a dislocationconcentration less than about 10⁷/cm² and the nitride working layercomprises one or more layers of GaN, AlN, AlGaN, GaAlN, InGaN, or GaInN.

In one arrangement, the working layer is a stack of deposits of GaN withdifferent types of doping, and the stack of GaN may be self supporting.The working layer may be InGaN; the seed layer GaN and the supportsubstrate sapphire. It is useful for the support and working layer toeach have substantially the same thermal expansion coefficient.

The seed and nitride working layers may be detached from the support bythe application of stress at the intermediate layer. Also, the seedlayer is typically provided on the support by implanting ions into asource substrate to form a zone of weakness at a depth that correspondsto the desired thickness of the seed layer, bonding the source substrateto the support, and detaching the seed layer at the zone of weakness bythe application of a force to transfer the seed layer to the supportsubstrate.

Advantageously, the method further comprises recycling the removedsupport for subsequent reuse. Also, the method can further includepreparing the seed layer to receive the nitride working layer, whereinthe preparation includes at least one of polishing, annealing,smoothing, oxidation, and etching.

Another aspect of a method for fabricating a semiconductor substrateaccording to the invention includes transferring a seed layer on to asupport substrate, depositing a working layer on the seed layer to forma composite substrate, and detaching the seed layer and the workinglayer from the composite substrate to form the semiconductor substrate.In this implementation, the material of the seed layer is suitable foraccommodating the thermal expansion of the support substrate and thethermal expansion of the working layer.

Preferably, the support substrate comprises a material having thermalexpansion coefficients that minimize stresses that arise duringvariations in temperature. Advantageously, the seed layer is transferredonto the support layer by molecular adhesion. In an implementation, theseed layer and the working layer are detached from the compositesubstrate by the application of stress at the adhesion interface,wherein the stress is selected from the group consisting of mechanicalstress, thermal stress, electrostatic stress and laser irradiationstress, or a combination thereof. This can be achieved through the useof a bonding layer of a material that absorbs the irradiation of thelaser on the support substrate prior to transferring to the seed layerthereto to facilitate subsequent detaching of the seed layer and theworking layer from the composite substrate.

In an implementation, the working layer is made of gallium nitride. Inaddition, the seed layer may be made of a material from the groupconsisting of sapphire, silicon carbide, zinc oxide, silicon, galliumnitride, neodymium gallate, and lithium gallate. The support layer maybe made of a material selected from the group consisting of siliconcarbide, aluminum nitride, silicon, and sapphire. Advantageously, theseed layer and the support layer have substantially the same chemicalcomposition.

The support substrate material preferably comprises amorphous materials,polycrystalline materials, and sintered materials. More preferably thesupport comprises materials such as polycrystalline silicon carbide,monocrystalline silicon carbide, polycrystalline aluminum nitride,polycrystalline gallium nitride, and monocrystalline gallium nitridehaving a high concentration of dislocations (greater than 10⁷/cm₂). Thematerials for both the seed layer and the support may have the samechemical composition.

In a beneficial embodiment, the method further includes applying anintermediate layer between the seed layer and the support. Theintermediate layer may be at least one of a bonding layer or aninsulating layer.

Preferably, the seed layer includes crystal lattice parameter(s)selected so that the epitaxially grown seed layer such that the workinglayer has a dislocation concentration less than about 10⁷/cm². Suchmaterials are known in the art and include nitrides such as GaN. Anadvantageous implementation includes providing a source substrateincluding the seed layer and a weakened zone, and detaching the seedlayer from the source substrate at the weakened zone. In thisembodiment, the weakened zone includes implanted atomic species at adepth that corresponds to the thickness of the source substrate, and theseed layer may be detached from the source substrate by application ofat least one of heat treatment, mechanical stress, thermal stress,chemical etching, or a combination thereof.

The seed layer may also be selected to obtain a precise crystalstructure and orientation, for example to obtain hexagonal or cubicgallium nitride, or if an Si face or a C face is selected to deposit theworking layer on a seed layer of silicon carbide; the seed layer is madeof gallium nitride of very high quality, i.e., having fewer than 10⁶dislocations per square centimeter, e.g., gallium nitride obtained by anepitaxial lateral overgrowth (ELOG) technique.

The method according to this aspect of the invention preferably furtherincludes preparing the seed layer to receive the working layer, whereinthe preparation includes at least one of polishing, annealing,smoothing, oxidation, and etching. The method may also advantageouslyinclude removing the support substrate such that it remains in acondition sufficient for recycling and reuse.

In this method, the working layer advantageously comprises a metalnitride, the seed layer advantageously comprises a material from thegroup consisting of sapphire, silicon carbide, zinc oxide, silicon,gallium nitride, neodymium gallate, and lithium gallate, and the supportsubstrate advantageously comprises a material from the group consistingof silicon carbide, aluminum nitride, silicon, and sapphire. Preferably,the metal nitride is GaN, AlN, AlGaN, GaAlN, InGaN, or GaInN and theworking layer is a stack of deposits of GaN with different types ofdoping. In some embodiments, the stack of GaN may be self supporting.Also, the working layer may also be InGaN with the seed layer GaN andthe support substrate sapphire.

The method may further comprise applying an intermediate layercomprising at least one of a bonding layer or an insulating layerbetween the seed layer and the support substrate. Typical bonding layerscomprise at least one of silicon oxide or silicon nitride. Also, theseed layer may comprise a material with a crystal lattice parameterselected so that the working layer has a dislocation concentration lessthan about 10⁷/cm².

The method may further comprise providing a source substrate includingthe seed layer wherein the seed layer is made of a material that absorbslaser radiation, and detaching the support substrate from the sourcesubstrate at the seed layer by the application of laser irradiationstress.

In another embodiment, the invention relates to a method for fabricatinga semiconductor substrate, which comprises providing a source substratewith a weakened zone defining a seed or nucleation layer and a supportsubstrate bonded thereto; depositing at least one working layer of asemiconductor material upon the seed or nucleation layer; providing atarget substrate upon the working layer of the deposited semiconductormaterial to form a support assembly comprising the target substrate, thedeposited semiconductor material, the seed or nucleation layer, andsupport substrate; and removing the support assembly by applying laserirradiation stress to the seed or nucleation layer to provide asemiconductor substrate comprising the at least one layer ofsemiconductor material on the target substrate.

In this method, the target substrate may be a thick layer deposited onthe working layer before irradiation detachment of the support assembly.Alternatively, the target substrate may be provided upon the workinglayer by metal bonding of the target substrate to the working layer.Preferably, the semiconductor material layer comprises gallium nitride,and wherein the nucleation layer is selected from the group consistingof silicon carbide, gallium nitride and sapphire, the intermediatesupport is selected from the group consisting of silicon, galliumarsenide, zinc oxide, lithium gallium oxide and lithium aluminum oxide,and the at least one bonding layer comprises at least one of siliconoxide or silicon nitride.

The weakened zone typically comprises implanted atomic species at adepth that corresponds to the thickness of the source substrate. Thus,the support substrate may be removed for subsequent recycling and reuse.Also, components may be formed on or in the working layer either beforeor after removing the support substrate.

In aspects of this embodiment, the material and the thickness of thenucleation layer are selected so that thermal expansion of the supportsubstrate and of the working layer occurs without significant damage;the semiconductor material layer is epitaxially deposited on thenucleation layer and the nucleation layer comprises a barrier layeragainst diffusion of atoms from the intermediate support at epitaxialgrowth temperatures; the intermediate assembly is removed by etching;and the providing step further comprises affixing the nucleation layerto the at least one bonding layer and to the support substrate bymolecular bonding.

In further aspects of this embodiment, the semiconductor material layercomprises gallium nitride; the nucleation layer is selected from thegroup consisting of silicon carbide, gallium nitride and sapphire; theintermediate support is selected from the group consisting of silicon,gallium arsenide, zinc oxide, lithium gallium oxide and lithium aluminumoxide; the at least one bonding layer comprises at least one of siliconoxide or silicon nitride; the weakened zone comprises implanted atomicspecies at a depth that corresponds to the thickness of the sourcesubstrate; and the support substrate is removes for subsequent recyclingand reuse.

Further aspects and details and alternate combinations of the elementsof this invention will be apparent from the following detaileddescription and are also within the scope of the inventor's invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention may be understood more fully by reference to thefollowing detailed description of the preferred embodiment of thepresent invention, illustrative examples of specific embodiments of theinvention and the appended figures in which:

Other aspects, aims and advantages of the present invention become clearfrom the following description of a preferred implementation, given byway of non-limiting example and made with reference to the accompanyingdrawings in which:

FIG. 1A illustrates an initial step of a method in accordance with anaspect the invention further illustrating source substrate 10 and seedlayer 12 each thermal expansion coefficient α_(S); FIG. 1B illustrates afurther step of a method in accordance with an aspect of the inventionfurther illustrating support substrate 20 and bonding layers 13 and 23with thermal expansion coefficients α_(P) and α_(B), respectively;

FIG. 1C illustrates a further step of a method in accordance with anaspect of the invention;

FIG. 1D illustrates a further step of a method in accordance with anaspect of the invention further illustrating working layer 30 withthermal expansion coefficient α_(w);

FIG. 1E illustrates a further step of a method in accordance with anaspect of the invention further illustrating target substrate 40 andmetallization layer 41 with thermal expansion coefficients α_(T) andα_(M), respectively;

FIG. 1F illustrates a further step of a method in accordance with anaspect of the invention;

FIG. 1G illustrates a further step of a method in accordance with anaspect of the invention;

FIG. 2A illustrates an initial step of a method in accordance withanother aspect of the invention further illustrating a source substratewith a thermal expansion coefficient α_(S);

FIG. 2B illustrates a further step of the method in accordance withanother aspect of the invention further illustrating support substrate20 with thermal expansion coefficient α_(P) where α_(P)≠α_(S);

FIG. 2C illustrates a further step of the method in accordance withanother aspect of the invention;

FIG. 2D illustrates a further step of the method in accordance withanother aspect of the invention further illustrating working substrate30 with thermal expansion coefficient α_(w) where α_(W)≠α_(S) andα_(W)≠α_(P);

FIG. 2E illustrates a final step of the method in accordance withanother aspect of the invention; and

FIG. 3 illustrates a version of the other aspect of the invention ofFIG. 2D in which the thermal expansion coefficients are in the relation0.7 α_(w)≦αα_(p)≦3 α_(w).

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Preferred embodiments of the invention are now described. It should beunderstood that the preferred embodiment using Bernoulli wands are notlimiting and other embodiments of this invention do not use Bernoulliwands. Headings are used herein for clarity only and without anyintended limitation.

The present invention preferably provides a method for fabricating asubstrate by hetero-epitaxial growth wherein the epitaxial layer(s) isprotected against contamination from the substrate material despiteexposure to the high temperatures necessary for growth. The inventionalso provides a method for easy removal of the support on which theepitaxial layer is grown.

Generally, when the intermediate support is a material that can bechemically attacked by a given attack medium, e.g., GAs, it ispreferable for the material of the nucleation layer to be one that formsa barrier against diffusion of elements deriving from any thermaldissociation of the intermediate support material. According to thepresent invention, it is also possible to select a substrate that is noteasily chemically removed, and to detach it using laser irradiation.This enables the substrate to possibly be recycled. For example,sapphire is a substrate that is transparent to laser irradiation and SiNcan be used as an absorbing bonding layer.

In one specific arrangement, the method involves epitaxial growing ofthe monocrystalline semiconductor material on the nucleation layer.Preferably, monocrystalline semiconductor material is deposited on thenucleation layer by epitaxy. However, other methods are suitable, as isknown in the art.

As noted above, the material of the intermediate support is one that canbe chemically attacked or etched by a given etching medium, it issubject to thermal dissociation when exposed to a the temperature ofepitaxial growing of the semiconductor layer, and is made of a materialthat is less expensive than materials that are more resistant to thermaldissociation at epitaxial growth temperatures.

Referring to FIGS. 1A to 1G, FIG. 1A shows a source substrate 10, suchas monocrystalline silicon carbide SiC, in which ions, e.g., hydrogenions, have been implanted at a certain depth using an ionic bombardmentmachine, a plasma implantation machine, or any other known method in theart. The implantation of ions defines a nucleation layer or seed layer12 of implanted ions on a portion of the source substrate 10, whereinthe main concentration of ions on the source substrate define adetachment zone or weakened zone 14. Typically, ions are implanted to adepth in the range of about 200 nanometers (nm) to 1000 nm, using ionswith energy in the range of about 50 kilo electron volts (keV) to 200keV, and an implantation dose in the range of about 5×10¹⁶ ions persquare centimeter (ions/cm²) to 1×10¹⁶ ions/cm².

Referring to FIG. 1B, substrate 10 having layer 12 is attached to anintermediate growth support substrate 20 by molecular bonding to form asource substrate-intermediate growth support substrate assembly. Forexample, the growth support substrate 20 may comprise monocrystallinegallium arsenide GaAs. Typically, the intermediate growth supportsubstrate 20 has a thickness in the range of about 400 micrometers (μm)to 800 μm.

Optionally, at least one surface of source substrate 10 and/or supportsubstrate 20 is provided with bonding layers 13, 23 in a manner known inthe art. The expansion of bonding layer is negligible due to its smallthickness compared with the thickness of the other layers (e.g., seed,working layers and substrates). Such bonding layers may be silicon oxideSiO₂ or silicon nitride Si₃N₄. However, other materials may be used asknown in the art. When formed from SiO₂ on Si, the bonding layer(s) areprovided on the surface of the source substrate or the intermediatesupport substrate by thermal oxidation, or alternatively, by deposition.The bonding energy of the bonding interface is brought to the requiredlevel by heat treatment, typically at a temperature of more than about300° C. for a period that is typically 2 hours. However, other knownmethods may be used.

Stresses, such as thermal, laser irradiation, and/or mechanical, butwhich could be of some other nature, are applied to the sourcesubstrate-intermediate growth support substrate assembly so as to detachthe intermediate growth support substrate 20 and the nucleation layer orseed layer 12 from the remaining source substrate 10, at the detachmentzone 14. Such detachment can be accomplished using the known Smart-Cut®technique developed by Applicant. To this end, a heat treatment istypically carried out at a temperature in the range 800° C. to 900° C.for a period in the range 30 minutes to 3 hours. Such heat treatment canbe combined with that used to strengthen the bonding interface.

As illustrated in FIG. 1C, a structure comprising a GaAs growth support20 having a thin nucleation layer 12 of monocrystalline SiC is obtained.The free surface of said layer can undergo polishing/cleaning and inparticular chemical-mechanical polishing or ion beam smoothing intendedto allow good-quality epitaxial growth to be performed thereon.

A metal organic chemical vapor deposition (MOCVD) hetero-epitaxytechnique is carried out on this surface to produce a stack of depositsof gallium nitride GaN with different types of doping, said techniquebeing known to produce a GaN stack or working layer 30 having goodcrystal quality.

Such technique is carried out at a temperature of about 1050° C. to1100° C., at which temperature partial dissociation of the GaAs of thesupport substrate 20 is observed. The presence of the SiC nucleationlayer 12, however, forms a barrier layer against the diffusion ofarsenic or gallium atoms towards the deposited layer 30, and therebymaintains the quality of the and the purity of layer 30.

The stack of GaN is typically a few microns thick, i.e., it is a thinlayer, as opposed to the thick layers with a minimum thickness of about200 μm to 300 μm, which renders the stack self-supporting.

FIG. 1D shows the resulting structure.

After growth of the GaN stack 30, the assembly comprising the supportsubstrate layers 20, bonding layer 23, bonding layer 13, implantinglayer 12 and layer 30 is applied to a target substrate 40 ofmonocrystalline or polycrystalline silicon so as to form the finalsupport of the GaN layer.

At its surface receiving the GaN layer, said final support 40advantageously has metallization 41 allowing the final support tocomprise a reflector for visible or UV radiation emitted by theelectroluminescent components which have been formed in the layer 30.The metallization 41 of the surface of the final support 40 ispreferably achieved by cathode sputtering or vacuum evaporation of gold,tin, or palladium (or of any suitable alloy) with a thickness of 500 nm,for example. The thermal expansion of the metallization layer isnegligible due to its small thickness compared with the thickness ofother layers (e.g., seed, working layers and substrates).

The free surface of the GaN stack 30 undergoes polishing treatment,typically a chemical-mechanical polishing or ion beam smoothing intendedto provide a flatness that is suitable for molecular bonding with thetarget substrate 40, which itself must have satisfactory flatness priorto metallization.

The thickness of substrate 40 is typically in the range of about 300 μmto 500 μm.

Fixing is achieved by molecular bonding or by eutectic bonding (whichmeans that polishing can be dispensed with), if necessary supplying heatenergy at a temperature in the range 200° C. to 350° C. for severalhours to produce the desired bonding forces.

Optionally, prior to fixing, the GaN stack 30 can undergo all or sometreatments for producing components such as blue or green LEDs, laserdiodes, etc.

When Gas is used as the intermediate substrate, the assembly is exposedto chemical attack with a solution comprising a mixture including HF,HNO₃, CH₃COOH, and H₂O in proportions of 1:3:3:5 to completely removethe intermediate GaAs support 20. Alternatively, it is possible to use asubstrate that is not easily chemically removed and in that event it canbe detached using laser irradiation. For example, sapphire is asubstrate that is transparent to laser irradiation and in that case SiNcan be used as an absorbing bonding layer that is fractured by the laserirradiation so that the sapphire substrate can be detached.

The nucleation layer, and if appropriate, the bonding layers 13, 23 (ifthey have not been removed chemically) are removed preferably by ionicetching. Additionally, it is also possible to remove a portion of theepitaxial layers that have been formed, in particular to remove initialepitaxial layers containing defects.

The method described herein with mention of certain examples is notmeant to be limiting, and as is known in the art variants are alsoencompassed within the invention. For instance, the choice of nucleationlayer 12 is principally conditioned by the search for a compromisebetween the lattice parameter, thermal expansion coefficient, stabilityat high temperatures, ability to form a barrier layer against thediffusion of elements from possible partial decomposition of the layerforming the intermediate support. Preferably, either SiC as indicatedabove is selected, or GaN, or even sapphire is selected. However, othermaterials may be used as known in the art.

The material of the intermediate support 20 is not critical as regardsto lattice parameter, but it should be selected principally as a resultof finding a compromise between its thermal expansion coefficientcompared with that of the material of the epitaxial layer, the stabilityof the epitaxial layer under high temperatures, and in particular thefacility with which it is removed chemically.

In addition to GaAs, other materials may be used such as silicon,certain oxides such as ZnO, LiGα₂ or NdGaO₃. Further, the materialdeposited by epitaxial growth to form the useful layer or layers of thesubstrate is typically a stack of differently doped layers of GaN, in amanner that is known in the art. However, it can also be a stack of avariety of other metal nitrides such as AlN or GaAlN, etc.

Finally, the final support 40 can be any support selected as a functionof a compromise between its ability to receive the metallization 41 ifappropriate, its ability to receive the deposited layer 30 by bonding orany other technique, its properties in terms of mechanical and chemicalstability during treatments for producing components in the stack oflayers 30, its thermal properties, its fabrication cost, etc.

Preferred embodiments of the invention relate to a substrate for optics,electronics, or opto-electronics, which comprises a seed layer of Si,monocrystalline SiC, sapphire, monocrystalline GaN, NdGaO₂, or LaGaO₂, abonding layer of SiO₂ or Si₃N₄ on the seed layer, and a working layer ofGaN, AlN, AlGaN, GaInN, or SiC on the bonding layer.

Table 1 below summarizes examples of materials that are suitable for usein implementing the methods of the invention described above. These areillustrative and should not be construed as limiting the features of theinvention.

TABLE 1 Seed layer 2 Bonding (typically layers 10, Working 1000 Å 11(typically Support 12 (typically layer 16 thick) 1 μm thick) 300 μmthick) GaN or AlN or Mono SiC SiO₂ or Si₃N₄ Poly SiC or mono SiC AlGaNor GaInN or sapphire or poly or SiC or other AlN or poly GaN GaN or AlNor {111} Si SiO₂ or Si₃N₄ Poly SiC or mono SiC AlGaN or GaInN orsapphire or poly or SiC or other AlN or poly GaN GaN or AlN or SapphireSiO₂ or Si₃N₄ Poly SiC or mono SiC AlGaN or GaInN or sapphire or poly orSiC or other AlN or poly GaN GaN or AlN or Mono GaN SiO₂ or Si₃N₄ PolySiC or mono SiC AlGaN or GaInN or sapphire or poly or SiC or other AlNor poly GaN GaN or AlN or NdGaO₂ or SiO₂ or Si₃N₄ Poly SiC or mono SiCAlGaN or GaInN LiGaO₃ or sapphire or poly or SiC or other AlN or polyGaN

In the above table, as in the tables below, the term “mono” is used tomean “monocrystalline” and the term “poly” is used to mean“polycrystalline”.

Another embodiment, not shown in the Figures, comprises two distinctlayers deposited on or applied to the intermediate support, one forminga barrier to the diffusion of elements deriving from dissociation of thematerial of the intermediate support, and the other, outer layer,forming a nucleation layer. It should be noted in this respect that thebarrier layer can be formed, deposited or applied either onto the sourcesubstrate 10, or onto the intermediate support 20, prior to bonding.

EXAMPLES

The following examples illustrate preferred embodiments of theinvention.

Example 1

A 500 nm thick layer of SiO₂ is produced on one face of amonocrystalline SiC source substrate by thermal oxidation. Hydrogen ionsare then implanted with an energy of 100 keV and using a dose of 8×10¹⁶ions/cm² into the source substrate using ion bombardment equipment. A500 μm thick monocrystalline GaAs substrate intended to form theintermediate support is also prepared, and one face of the substrate iscoated with a 500 nm thick SiO₂ layer by chemical vapor deposition.

Surface activation is then carried out, for example bychemical-mechanical polishing, to smooth the surfaces and provide themwith a certain hydrophilic nature. The faces of the source substrate andthe intermediate support substrate are then brought together and bonded,and a suitable bonding energy is obtained by heat treatment at 350° C.for a period of 2 hours.

This assembly then undergoes heat treatment at 900° C. for a period ofone hour to obtain detachment at the implanted zone. The face of thelayer 12 is then polished at the detachment location using ionicsmoothing by ion cluster smoothing.

Different GaN layers are then deposited by epitaxial growth. Typically,the GaN stack 30 has the following succession of layers: an 8 nm AlNbuffer layer, and a 1 μm GaN layer.

After the operation, the free face of the stack 30 is polished by usingan ion cluster technique.

Meanwhile, a monocrystalline silicon substrate with a normal commercialgrade of surface polishing and a thickness of 500 μm is coated with ametallization layer based on indium/palladium over a thickness of 400nm. The intermediate support 20 carrying the stack 30 and the substrate40 carrying the metallization 41 are then bonded together by molecularbonding, the bonding interface being reinforced by heat treatment at350° C. for a period of 2 hours. The GaAs intermediate support is thenattacked by immersion in an attack solution composed of a mixture of HF,HNO₃, CH₂COOH, and H₂O in proportions of 1:3:3:5, peripheral attack ofthe metallic layer 41 being minor and without consequence. The attackfinishes at the SiC layer 12. This latter layer is then removed, forexample by SF₆/O₂ reactive ionic etching.

Example 2

In accordance with another aspect of the invention, referring to FIGS.2A to 2E, the technique includes transferring a nucleation layer or seedlayer 12 onto a support substrate 20 (illustrated in FIG. 2C),depositing a semiconductor layer or working layer 30 on the seed layer12 to form a composite substrate (illustrated in FIG. 2D), and thendetaching the seed layer 12 and the working layer 30 from the compositesubstrate (illustrated in FIG. 2E). The seed layer in accordance withthis aspect of the invention may comprise material such as sapphire,silicon carbide, zinc oxide, silicon, gallium nitride, neodymiumgallate, lithium gallate, or any combination thereof. Also included areother materials commonly known in the art. In an implementation, theseed layer 12 is prepared before receiving the working layer, whereinthe preparation may include polishing, annealing, smoothing, oxidation,etching or any combination thereof.

Preferably the material comprising the seed layer has a crystal latticeparameter selected to that a working layer that is grown on the seedlayer has a dislocation concentration less than about 10⁷/cm².

Also in accordance with this aspect of the invention, the sourcesubstrate includes a seed layer 12 and a weakened zone 14 (illustratedin FIG. 2A). In this embodiment, the seed layer 12 is detached from thesource substrate 10 at the weakened zone 14, and transferred onto asupport substrate 20 (illustrated in FIGS. 2B-C). The detached seedlayer 12 is transferred onto the support substrate 20, for example, bymolecular adhesion at an adhesion interface 16. A working layer 30 isdeposited onto the transferred seed layer 12 to form a compositesubstrate (illustrated in FIG. 2D). The seed layer 12 and the workinglayer 30 are detached from the composite substrate at the adhesioninterface 16 (illustrated in FIG. 2E).

The depositing step may include depositing the seed layer onto thesupport substrate by epitaxy. However, other methods as known in the artmay be used. Also, the seed layer and the working layer may be detachedfrom the composite substrate by the application of stress.

Optionally, the invention may further include applying a first bondinglayer 13 onto the source substrate 10, and applying a second bondinglayer 23 onto the support substrate 20. Preferably, the source substrate10 includes implanted atomic species to a predetermined depth to form aweakened zone 14. The first and second bonding layers 13, 23 may becontacted to attach the source and support substrates, and then the seedlayer 12 can be detached from the source substrate 10 at the weakenedzone 14 and then transferred onto the support substrate 20. Thereafter,the working layer 30 may be deposited onto the seed layer 12, which hasbeen transferred to the support substrate 20.

Advantageously, detaching steps occurring in the methods of thisinvention can include applying a stress such as mechanical stresses,thermal stresses, electrostatic stresses, laser irradiation stresses, ora combination thereof. If desired, the support may then be recycled andreused.

In yet another variant of the method of the invention, the working layer16 of gallium nitride is substituted by a working layer 16 of aluminumnitride, of silicon carbide, an alloy of aluminum and of gallium, andalloy of gallium and indium such as InGaN, or another nitride or carbidecompound. The working layer 16 of gallium nitride can also besubstituted by a multilayer structure constituting a stack of layers ofthe gallium nitride, aluminum nitride, gallium and indium nitride, etc.types, possibly having different kinds of doping, etc.

In another variant, all or some of the components on the working layer16 are made either before or after removing the support 12.

Example 3

In another embodiment of the method of the invention, a structure isprovided comprising a working layer on a seed layer itself on a supportwith bonding layers and interposed between the seed layer and thesupport. A thick layer is deposited on the free surface of the workinglayer and the support is removed, either alone or together with the seedlayer. The thick layer then serves in particular to support the workinglayer, after the seed layer support has been removed.

In this embodiment, the further layer of the substrate is present uponthe working layer on a face opposite that of the seed layer, wherein thefurther layer preferably is polycrystalline SiC, polycrystalline AlN,polycrystalline GaN, boron nitride, diamond or a metal such a copper.

Table 2 below summarizes examples of materials that can be used in thecontext of this second implementation of the method of the invention.These examples are purely illustrative and should not be construed aslimiting.

TABLE 2 Bonding Working layer layers 16 Seed layer 2 10, 11 Support 12Thick layer 4 GaN or AlN or {111} Si or SiO₂ or Poly SiC or Diamond orAlGaN or mono SiC or Si₃N₄ poly AlN or poly SiC or GaInN or SiC GaN orsapphire or GaN or AlN or or other sapphire or mono SiC or boron nitrideor NdGaO₂ or poly GaN metal (copper) LiGa₃

In the preceding examples, the support substrate preferably comprises amaterial having a coefficient of thermal expansion of about 0.7 to 3times the coefficient of the working layer. Preferably, the seed layercomprises a material so that throughout the expected range oftemperatures neither the support nor the working layer is significantlydamaged (e.g., by cracking, flaking, separation, increased dislocationdensities, and the like). The effect of the coefficient of thermalexpansion of the seed layer is insignificant in the structure as thelayer is very thin compared to the thickness of the working layer andsupport substrate. This small thickness allows to avoid any damaging inthe working layer during temperature changes as during the epitaxy.

Preferably, the values of the thermal expansion coefficients hereinrelate to those in a plane parallel to the plane of the working layer.Advantageously, the material selected to form the support presentsthermal expansion coefficients that reduce or even eliminate significanttension or compression stresses of the kind that arise during thevariations in temperature that are inherent when growing the workinglayer, or that occur when the substrate formed in this manner returns toambient temperature.

Importantly, tolerance to the differences of the thermal expansioncoefficients of the working layer and the support substrate materials,increases when these differences lead to compression in the workinglayer, as opposed to when it leads to stretching of the layer. Thus,thermal expansion coefficient of the support material can be severaltimes greater than that of the working layer and that leads tocompression of the working layer when temperature is cooling down afterepitaxy. However, the thermal expansion coefficient of the supportmaterial is preferably not less than 0.7 times the coefficient of theworking layer as the working layer is also stretched or extended whencooling down in this case.

Preferably, the nucleation layer or seed layer is selected such thatthermal expansions of the support and/or the working layer do not causesignificant wafer damage. For this purpose, the seed layer has athickness that is small enough to enable it to be deformed so as toaccommodate the dimensional variations due to thermal expansion of thesupport and/or of the working layer. This thickness depends on the seedlayer material and on the respective materials of the support and of theworking layer.

For example, a difference in the thermal expansion coefficients of theworking layer and support substrate leads to a certain linear expansionor contraction of the seen layer. Then depending on the coefficients ofelasticity of the seen layer, this linear expansion or contraction inturn leads to a force in the seen layer and its boundaries. If thisforce is small, flaking, fracturing, dislocations, and other damage(collectively, “damage”) will not occur. Accordingly, one of ordinaryskill in the art can readily determine an appropriate thickness for theseed layer by simply trying seed layers of various increasing ordecreasing thicknesses. As used here, the phrase “the seen layeraccommodates” means a seed layer that is not damaged by expansion andcontraction of the working layer and the support substrate. And thephrase “a seed layer sufficient to accommodate” means a seed layerhaving physical properties (e.g., thickness and coefficients ofelasticity) with respect to the physical properties of the working layerand the support substrate (e.g., coefficients of thermal expansion) sothat significant damage does not occur to either the working layer orsupport substrate.

Typically, for a silicon carbide support having thickness of 300 microns(μm) and a gallium nitride working layer having thickness of severalmicrons, a monocrystalline silicon carbide seed layer should havethickness that is less than 0.5 μm, and that is preferably less than1000 angstroms (Å).

Advantageously, as mentioned above, the seed layer material alsopresents lattice parameters such that the working layer can beepitaxially grown on the seed layer with dislocations in the workinglayer at a concentration of less than 10⁷/cm². The skilled person knowshow to select such seed materials (ex., GaN) and epitaxial growthparameters and orientations (ex., epitaxial lateral overgrowthconditions, primarily vertical growth conditions, lower depositiontemperatures) both for the seed layer and for the working layer.

Clearly, the present invention is not limited to the preferredimplementations described and shown in the drawings, and the skilledperson is capable of providing variants and modifications, all of whichare included within the scope of the appended claims.

The words “significant” and “likely” are used here to mean withinacceptable and expected limits for the intended purpose. Often these arecommercial purposes and commercially-acceptable limits, but commercialapplications are not limiting. For example, in the phrase “significantwafer damage is unlikely in the process”, the phrase “significant waferdamage” is taken to mean damage that limits or prevents intended uses,usually fabrication of devices on the wafer. This is necessarilyrelevant to the context in which the process is practiced, butnevertheless in all cases, can be readily determined by one of ordinaryskill in the art.

Other words of degree are interpreted similarly. For example, the word“substantially” as used in the phrase “A is substantially the same as B”is taken to mean the A and B are the same within normal and expectedtolerances, e.g., commercial tolerances, research tolerances, and thelike. For example, the phrase “unlikely in the process” is taken to meanthat, although significant damage may occur, it occurs sufficientlyrarely that economical use of the process is not hindered or prevented.For example, greater the 98%, 95%, 90%, 85%, of the wafers are free ofsignificant damage, the exact percent allowable varies in dependence on,e.g., the cost of the wafer.

The ranges signified by these terms depend on commercial requirements(or research requirements, or the like) and can vary but in all casesare not to be construed and imposing requirements beyond what arecurrently achievable given a current state-of-the-art. It should beunderstood that this invention is not limited to commercial uses;intended uses include research uses, special purpose uses, and so forth.

The preferred embodiments of the invention described above do not limitthe scope of the invention, since these embodiments are illustrations ofseveral preferred aspects of the invention. Any equivalent embodimentsare intended to be within the scope of this invention. Indeed, variousmodifications of the invention in addition to those shown and describedherein, such as alternate useful combinations of the elements described,will become apparent to those skilled in the art from the subsequentdescription. Such modifications are also intended to fall within thescope of the appended claims.

1. A method of making a semiconductor substrate which comprises:providing an support that includes a barrier layer thereon forpreventing loss by diffusion of elements derived from dissociation ofthe support at epitaxial growth temperatures; providing a seed layer onthe barrier layer, wherein the seed layer facilitates epitaxial growthof a single crystal III-nitride semiconductor layer thereon; epitaxiallygrowing a nitride working layer on the thin seed layer; and removing thesupport to form the substrate.
 2. The method of claim 1, wherein thesupport is made of a sintered or polycrystalline material.
 3. The methodof claim 2, wherein the support comprises a polycrystalline siliconcarbide, monocrystalline silicon carbide, polycrystalline aluminumnitride, polycrystalline gallium nitride, or monocrystalline galliumnitride having a concentration of dislocation that is greater than10⁷/cm².
 4. The method of claim 1, wherein the barrier layer comprisessilicon nitride.
 5. The method of claim 1, wherein the seed layercomprises sapphire, silicon carbide, zinc oxide, silicon, galliumnitride, neodymium gallate, or lithium gallate.
 6. The method of claim1, wherein the seed layer comprises a material with a crystal latticeparameter selected so that the nitride working layer has a dislocationconcentration less than about 10⁷/cm².
 7. The method of claim 1, whereinthe nitride working layer comprises one or more layers of GaN, AlN,AlGaN, GaAlN, InGaN, or GaInN.
 8. The method of claim 7, wherein theworking layer is a stack of deposits of GaN with different types ofdoping.
 9. The method of claim 8, wherein the stack of GaN is selfsupporting.
 10. The method of claim 1, wherein the working layer isInGaN; the seed layer is GaN and the support substrate is sapphire. 11.The method of claim 1, wherein the support and the working layer eachhave substantially the same thermal expansion coefficient.
 12. Themethod of claim 1, wherein the seed and nitride working layers aredetached from the support by the application of stress at theintermediate layer.
 13. The method of claim 1, wherein the seed layer isprovided on the support by implanting ions into a source substrate toform a zone of weakness at a depth that corresponds to the desiredthickness of the seed layer, bonding the source substrate to thesupport, and detaching the seed layer at the zone of weakness by theapplication of a force to transfer the seed layer to the supportsubstrate.
 14. The method of claim 1, which further comprises recyclingthe removed support for subsequent reuse.
 15. The method of claim 1which further comprises preparing the seed layer to receive the nitrideworking layer, wherein the preparation includes at least one ofpolishing, annealing, smoothing, oxidation, and etching.